Syntheses and Magnetic and Conductive Properties of New Low-Dimensional Complexes

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Phthalocyanines (Pcs) are well known to show remarkable increase in electrical conductivity on their partial oxidation, being originated from continuously stacking of the phthalocyanine rings based on the enhanced π-π interaction. However, the conductivity abruptly decreases when the temperature is lowered, which is explained in terms of Peierls-transition. In this research, a dinuclear copper (II) phthalocyanine ([CuPc(t-Bu)_3]_2) was newly prepared for investigation on ability of the dinuclear phthalocyanine complexes to get rid of the Peierls problem by giving rise to interaction other than the π-π one in the stacked structure. The observed intramolecular Pc-Pc interaction indicated that the dinuclear Pcs would be promising for developing low-dimensional materials in this way. However, no significant intramolecular magnetic interaction between the metal ions was observed although the interaction is considered to play an important role for the properties of the low-dimensional compou … More nds. The investigation on the other paramagnetic metal ions with dinucleating phthalocynine ligands will be performed.Polymer complexes have been prepared using dinuclear metal complexes M_2(O_2CR)_4 (M = Ru(II,III), Rh(II), Mo(II)) and various bridging ligands. The ruthenium (II,III) dimers have three unpaired electrons. Reactions with nitroxide radicals gave polymers of ruthenium (II,III) dimers axially linked by the radicals. The magnetic data showed strong interactions between the dimers and radicals, though an expected ferrimagentic property based on the alternated S=3/2 (for Ru_2) and S=1/2 (for nitroxide) arrangement was not observed. The rhodium (II) dimers were linked with pyrazine, 4, 4'-bipyridine, and 1, 4-diazabicyclo [2.2.2] octane. The polymer structure was confirmed by X-ray crystal analysis for the bipyridine complex. The molybdenum (II) polymers with p-quinones (9, 10-anthraquinone, 1, 4-naphthquionone, and 2, 6-dimethyl-1, 4-benzoquinone) were also prepared. The detailed analyses based on their X-ray structures indicated existence of interactions between the dimers and p-quinones. The above obtained results implies that the dimer complexes having metal-metal bonds are useful building blocks for metal-assembled complexes in combination with linkage ligands. Less